Apparatus for producing hydrogen.



A. MESSERSCHMITT. APPARATUS FOR PRODUCING HYDROGEN.

APPLICATION FILED JUNE 26. 1912.

Patented May 8, 1917.

3 SHEETS-SHEET 1.

A. MESSERSCHMITT.

APPARATUS FOR PRODUCING HYDROGEN. APPLICATION FILED JUNE 26.1912.

31. ,%%5,262. I Patented May 8, 1917.

3 SHEETS-SHEET 2.

A. MESSERSCHMITT.

APPARATUS FOR PRODUCING HYDROGEN.

APPLICATION FILEDJUNEZG. 1912.

Patented May 8, 1917.

3 SHEETS-SHEET 3.

ZWWZQQF Specification of Letters Patent,

Patten dMay 8, 191m.

Applicafion filed JimeBB, 1912- serial No. 706,118.

f To all whom it may concern.-

Be it known that L Dr. AN'roN ME- sonm'r'r, a subject of the Emperor ofGermany, and residin at No. 60 Rathhausstrasse, Stolberg, ermany, haveinvented certain new and use which the following is a specification.

This invention relates to apparatus for producing hydrogen; and itcomprises a re-- action chamber, a charge of active ferruginous materialin said chamber, a fur- -nace chamber in heat imparting relationship tothe reaction chamber, means for supplying steam, air and reducing gasand means whereby the steam and reducing gas currents may be passedthrough either the reaction chamber or the furnace chamber,

or both successively; and it also comprises in such an apparatus avertical tubular reaction chamber in heat receiving relationship to avertical furnace chamber said reaction chamber being somewhat shorterthan said furnace chamber to furnish communication between the same atone end;

all as more fully hereinafter set forth and as claimed.

Apparatus usually employed for commercial production of hydrogenvare oftwo general types; the retort type and the producer type. Both of thesetypes of apparatus possess disadvantages which it is the object of thepresent invention to overcome.

The retort type of apparatus usually comprises iron cylinders providedwith a refractory jacket and in use such cylinder is heated externallythrough the jacket during the heating phase of the process as is wellunderstood. Owing to the presence of the jacket the transfer of heatconducted to the reaction material contained in the. retort is impededand therefore in order to obtain the required temperatures in thereaction material the temperature in-the heating chamber surrounding theretort is necessarily kept very hi h. The wall temperature isnecessarily hig er than the core tem era ture. Frequently localoverheating o the charge results and this in turn results; in localfusion of the reaction material so-that it conglomerates more or lessand forms a mass WlllCll the steam and reduclng gas cannotreadily'permeate. The producing. ca-

Improvements in- Apparatus for Producing Hydrogen, of

area. of active surface exposedto the draft current. Fused metal is alsoapt to adhere and fuse to the retort walls with the result thatfrequently it has to be removed therefrom or a new retort su plied. Inan attempt to eliminate the sadvantages arising from the use ofjacketediron retorts in some instances the jackets have been dis- 'pensed withbut such unjacketed retorts have proved im racticable because theybecome damaged in a short period of time at the temperature imparted bythe action of the flame and under the continuous oxidizing efiect of thefurnace gases to which they are subjected. These retorts are usuallyused in furnace chambers in which there is a lack of suitable means formaintaining an equilibrium of pressure inside and outside the reactionchamber; within the reaction chamber and within the heating chamber.With unequal pressure in the heating chamber and in the reactionchamber, the gases used during the process permeate freelythroughthewalls of the 1ron retort.

. The producer type of apparatus usually comprises aniron retort orreaction chamber located in a gas producer in such manner that theretort is directly heated by the sensible heat of the ignited coke inthe producer while the hot gas generated in the producer in the ordinaryway is. admitted directly into the retort in order to reduce the ferrousmaterial. The iron=.is"subsequently'oxidized with a production ofhydrogen bymeans of steam admitted into the retort through separate pipecoils. Ow:

ing to the unavoidable and considerable temperature fluctuation in theco'ke'ch'arge incident to the operation of the producer and the combinedattacksofheat, coke, slag,

steam and air on the retort' material, .the use of'such producer type ofapparatus has not been particularly successful. called producer type ofapparatus may be said to also include a form' in which large producerchambers or shaft furnaces have been filled with the reaction materialand which in use have been subjected to direct The soneighborhood of theheating zone while the remoter zones are relatively cool. In spite ofstrong heating this type of apparatus does not succeed in storing usuificient heat in the ferrous charge, so t at the reaction soonweakens, and at too low temperature ceases altogether. Another importantdrawback of this type lies in the fact that the ferrous charge is madeso impure bythe large quantity of hot gases passing through, that itsoon loses its activity.

The present invention ehminates the objectionable overheating and unevenheating of the reaction material, the fusing of the reaction mass toitself and to the sides of the retort, which are incidental to hithertoknown hydrogen producing apparatus, while at the same time the presentinvention retains all the advantages of the known processes and securesadditional advantages such as the production of purer hydrogen and a lowconsumption of reducing gas and steam.

In the accompanying drawings showing several forms of specificembodiments of my invention, Figure 1 is a vertical section of one form;Fig. 2 is a vertical section of a modification; and Fig. 3 is a similarview of a somewhat different form from that shown in Fig. 2.

Referring first to Fig. 1: 1 indicates a heating chamber wall which ispreferably made of suitable refractory material adapted to Withstand andto store the heat incidental to the process. This chamber is providedwith a vertical preferably loosely but air-.

tight connected reaction chamber in the form of a cylinder 2 having nearits upper end the flange 3 which maintains it in de pending position inthe heatin chamber 1. This reaction chamber is imper orate except at itslowermost end 5 where it is provided with a cylindrical grating orscreen which prevents the reaction material from falling into theheating chamber 4, but which allows easy passage of the various draftcurrents. The heating chamber is provided with the refractory lining 6comprising a checkerwork or labyrinth of firebrick or, other fireproofmaterial which converts the heating chamber into a superheating and heatstoring inclosure. I

The upper end of the column or reaction chamber 2 is provided with achargin opening which may be closed by means 0 a cover 7. The lower endof the heating chamber 4 is in communication with an air box 8 (having acover 9) by means of radially projecting tubes or conduits 10 which havefor their purpose to supply air from the box 8 to the heating chamber 4.The box is closed at the bottom by means of a removable cover 11 whichis fitted with a pipe connection 12 leading to a source of air underpressure. A gate valve; -13" is provided for regulating the air supphedto this box.

Arranged concentrically with the box 8 there is an annular gas casing 14from which rise vertical pipes 15 and 16 adapted to supply gas todifferent levels in the heating chamber 4. These pipes 15 and 16 areuniformly distributed around the casing 14 and are so arranged that thelong pipes 16 alternate with the short ones 15. Valves 17 operated fromthe outside serve to control the supply of gas to these pipes. Thisannular casing 14 is in communication through a branch pipe 18 with themain gas pipe 19 which communicates at 20 with the top of the reactionchamber or column.

The box 8 may be supplied with steam from a pipe 21 connected with thechimney 22 by means of the pipe 23. At the junction of the pipes 21 and23 there is provided a 3-way cook 24 by means of which the steam can becaused to pass either through the pipe 21 or the pipe 23. The valve 25beyond the valve 24 serves for the purpose of shutting off steam whendesired.

From the main gas pipe 19 there branches an auxiliary waste/gas' pipe27, provided with a valve 28, and leading to a steam boiler furnace (notillustrated) or other place of use.

From the pipe 27, a pipe 29 branches downward into a vessel 30 providedwith a water seal. A pipe 33 serves for the removal of the hydrogen fromthe vessel 30.

In the use of the form of my invention shown in Fig. 1 the furnace orchamber 4 is heated by combustion of gas derived from any suitablesource through pipe 19, the chimney register 31, the gas valve 26 andthe air valve 13 being open. The gas enters the heating chamber throughpipes 15 and 16 and is burnt by air from the radial pipes 10. The heatof combustion enters the reaction material in chamber 2 by conductionthrough the wall. The waste gases escape through the open valve 31 intothe chimney. As soon, as the furnace is at red heat, and the reductionmaterial inside the column at a corresponding temperature, the reductionof the material can take place. By now opening the valve 32, reducinggases, if necessary previously heated; are admitted through 19 and 20into the top of the column and pass downward through the hot reactionmaterial, reducing it.

The waste gas escaping from the open lower end of the column passesupward through the heating chamber 4 and thence through the register 31to escape. With sus pended columns of the type shown this waste gas,particularly when it is combustible, is

e sees On the otherhand the reduction reaction;-

can be carried oiit with a high degree of superheat of the reducinggases, by changing the directionof flow just stated and passlng thegases through t e pipes 15- and through 20, 19 and 2 past the open valve28, to a steam boilerfur'nace in which they may be completely burnt. u

The reduction process s preferably so conducted that the two d1rectionsof gas flow alternate, which greatly assists the oh-' taining of auniform: heat distribution within the column, and therefore a uniformre: v

duction of the whole of its contents.

' When the reaction material is reduced to spongy iron, oxidation andproduction of hydrogen take place by means of steam, the iron beingconverted into ferroso-ferric oxid, with liberation of hydrogen. Forthis puropening the steam valve 25 and adjustment of the three-way cock24, the gas and air valves being closed. The steam flows from the box 8through the pipes 10 into and rises upward through the heating chamber4.- The chimney register 31 is kept 0 en mean-- while in order that thegases chamber and displaced upward can escape.

Hing the After steam has blown through suficiently to displace suchgases the register 31 1S closed. lhis leaves the chamber full of steamsuperheated by contact with the refractory material. The three-way cook24 is now so adjusted that the steam flows through the pipe 23 to thetop of the heating chamber and downward thercthrough, forcing before itthe very hot steam of the chamber. This steam, highly superheated bypassing through the heating space, enters the column at its open andlower end and flows upward therethrough, forming hydro-- gen and oxid ofiron. T e liberated hydrogen in the column is forced downward throughthe pipes 19 and 27 into the water seal vessel 30, (valve 28beingclosed), from which after overcoming the pressure of the head of water,it passes away through the pipe 33. to a place ofuse or storage (not 55shown).

The apparatus therefore provides for the operation of a processconslsting of a heating stage, a reducing stage and an'oxidizing andhydrogen forming stage, the reducing and oxidizing stages alternatingwith each other regularly while the heating stage may be interpolated asoften as required to keep up the temperatures. If desired the heatingstage can be ,combined with the; reducing stage when admission ofvreducmg gases.

' charge.

above described and when the emerging gases are burnt in the heatingchamber By inclosing the column in a closed gastight furnace, so thatboth the reaction space and the furnace space are practically in directcommunication not only is-a great pressure diderence between the columnand the furnace obviated, thereby rendering leakiness of the former ofno importance, but alsolosses of hydrogen gas, which were veryconsiderable in the retort rocess owing tovthe permeability of red hotiron to hydrogen and which took place on the slightest damage of therotor-ts, become quite impossible, since the red hot column wall doesnot constitute a partition between the hydrogen and the atmosphere, thecold outer wall of the furnace being the surface inclosing the apparatusfrom the outside. Hydrogen has a very rapid rate of difiusion. In thiscase however since steam surrounds and enters the retort any pressuredifferential between the spaces inside and outside the retort does nottend to cause leakage of hydrogen.

Direct heating of the iron charge by combustion in contact with it andconsequent rapid fouling of the charge and local overheating andnon-uniform temperature of the whole charge, such as are present withshaft "furnaces, are avoided in the use of the present apparatus.

.Whereas a generator shaft provided with "an iron charge can be heatedonly after the om'dation and hydrogen generating is finished and by a secially interpolated stage, while during orb heating stage is im ossiblesince the spongy iron would be reoxidized, in the present apparatus bythe production of the several compartments, heating can take placeindependently of the condition of the iron A considerable amount of heatis stored up in the refractory sides of the furnace and the firebrickchecker, the radiation and conduction from which prevents thetemperature in the column from falling too low when the heating stage isnot in progress, a feature which is of great importance and actscompensatingly at the difierent stages of the process.

This use of the furnace as a superheater allows the superheating of thesteam and,

to some degree that of the gas to be effected.

The fact of the reaction column being open at one end enables the heatedgases to be directly admitted to the column without loss of heat, and tobe brought into reaction with a ferrous charge, while badly actingjoints and valve devices are eliminated.-

At thesame time constructional difliculties originating from the greatexpansion and extension of the red hot retorts, are ob viated by usingvertically hung retorts free etwecn the other stages a at the lower end,and the charg'ng, emptying, and exchanging of the retorts arefacilitated.

Finally the combination of the furnace In the apparatus illustrated inFig. 2 a

pair of concentric cylinders 34 and. 35 each open at one end, arearranged in the furnace 1. The ring shaped space 36 formed between thetwo cylinders serves to receive the ferrous charge. The furnace space 37surrounding the outer cylinder and the furnace space 38 inclosed by theinner cylinder, are provided with brickwork checkers 39. To fill thereaction space lateral openings 40 with covers are provided, and'otherlateral openings 41 with covers, for the emptyi of the said space.

ith this type of apparatus the process is carried out in the followingmanner:

. The valve 42 is opened and reducing gas is admitted through the pipe43 to the top of the annular space 36. The gas admitted flows downwardthrough this space, reducing the hot om'd and traversing the bottomopening of the same and entering the inner heating space 38. Onemerging, it is still combustible. For the combustion of this gas, airis admitted'through the box 47 and the pipes 48 to the inner heatingspace 38,

the cover 44 being open to permit escape of waste products and the airadmission controlled by a valve 46. At the same time the outer furnacespace 37 can be heated by opening gas valve 50 and burning gas in suchspace with the air from the box, the

gas being supplied at different levels by pipes 15 and 16. Cover 45 isremoved to permit escape of products of combustion.

The covers 44 and 45 and the valve 42 are then closed, and by openingthe valves 49 and 50 the reducing, gas is admitted simultaneously to theouter and inner heating spaces 37 and 38. The gas penetrates thereaction space'36 after which it is conducted through the pipe 43 forcombustion under a steam boiler, not illustrated. The valves 49 and 50are closed and the valve 51 opened to admit steam for the purpose ofscavenging the apparatus. The cover 44 and then the passes upwardforcing before it the waste gases. The valve 51 is then closed and byopening the valve 52 the steam from the steam pipe 53 is sent into theapparatus, forcing ahead of it the superheated steam remaining inchamber 37 This hot steam passes through the ferrous material in themama's column, forming hydrogen. The hydrogen formed escapes through thepipe 43 into a receiver, not illustrated.

Fi 3 illustrates a type of apparatus, in whic a cylinder 54 open at oneend 1s fitted gas-tight to the bottom furnace wall, and a second 0linder 55 also open at one end and surroun is fitted gas tight to thetop furnace wall, so that the outer chamber 37 is in .communica-. tionwith the inner chamber 38 through the reaction space 36.

Annular burner passages 56 are provided for heating the inner furnacespace or stove. The inside of the stove is accessible through a door 57,and at the outer circumference of the furnace are provided doors 41 forthe emptying of reaction material.

The furnace of Fig. 3 can be operated as.

outer space 37, becoming thereby super-- heated, and thence into thereaction space 36, and traverses the same inwardly reducing the iron.The waste gasesthen pass to the chimney through the open cover At thesame time the inner superheater space 38 can be heated by internalcombustion as required by opening gas valve 59 and admitting air byopening the air valve 60.

Hereafter the cover 44 and the air valve 60 are closed, while the cover45 is opened, the effect of through the valve 59 flows upward-throughthe hot checkerwork and the reaction column in reverse direction, thatis downward, and escapes at the lower end of the outer cylinder, intothe outer furnace space 37. By opening the valve 61 air is admitted tothe annular chamber 62, whence it reaches the outer furnace space 37 sothat the reducing ng the cylinder 54 concentrically,

which is that the gas admitted gas issuing from the bottom of thereaction are closed. Afterthe inner heating space 38 has been blownthrough, the cover 44 is closed, the cover 45 opened, and by opening thevalve 63 and suitable adjustment ofthe three way cook 64 steam isadmitted through the pipe 65 to the lower part of the outer cover 45 areraised meanwhile. Steam heating space 37. After this steam has ex--pelled all foreign gases, the cover 45 is messes c Pes through the pipeinto a suitable re the iron charge in thin annular la ers and the apossibility of heating the said 0 arge from two sides, using a singlereaction charge, exceptionally large outputs of hydrogen can beobtained. Further there is ditional advantage thatthe interpolation ofseparate heating stages can be quite dispensed with, so that time issaved and consequently the output of the apparatus increased, andincidentally there is practically no limit to the size of apparatus thatmay be used as there will always be a relatively narrow annulus ofreaction material in this form of apparatus.

The described processes are obviously only examples. By means of thesefurnaces the preparation of the gas can be carried out in numerousmodified manners. It is obviously possible instead of two cylinders, toarrange a number of the same concentrically to each other and utilizethe spaces between the cylinder walls as alternately operating heatingand reaction spaces.

The choice of the reaction material for the reaction spaces is of thegreatest importance for the carrying out of the process by thisapparatus. In the present case the retorts or reaction columns can bemade of any fireresisting or refractory material since the difference ofpressure between the furnace space and the inside of the retort orcolumn is insignificant and the wall of the column is not required toresist the passage of gas under pressure. Under these circumstanceshowever, to obtain suficient transmission of heat from the heated outersides, the furnace or su erheater chamber must be kept at much ighertemperatures. than are actually required for the reaction.

The retorts or columns may be made of unprotected iron. Theheattransmission is then so rapid that not only is very little time lostby the periodic heating and the om'dation stage in particular muchshortened but also the temperature of the furnace can e kept lower. Bythis means the'output per hour of hydrogen by the apparatus isincreased, the danger of damage to the ferrous charge eliminated, andthe material of the columns rotected... .When unpro-' tected iron is usethe disadvantage of iron retorts, the rapid destruction of the same byoxidation, would make itself felt, were it not for another circumstancewhich allows this disadvantageto be obviated. The circumstance consistsin that with the present apparatus it is possible to periodically washthe columns both external y and internally with a stream of reducing.gases. It has been roved that with such treatment even bare iron retortsor columns can be preerived the adwith bricks containing iron oxid' orcasing.

served for exceptionally long periods, since the superficial ironoxidized by the furnace gases and steam is always reduced aga1n,. theinnercore of the iron protected, and its strength and cohesionpreserved. j

For aeronautical purposes it is well hown that the greatest purityof'the hydrogen is required. Owing to cavities and orosity of therefractory material it is di cult however to prevent the presencg ofsmall amounts of foreign ases in the hydrogen, owing to ineiiicienthlowing through. To drive out any remaining gas from even the smallestpores, according to a further pro-' cedure possible with the apparatusof this invention, the heating chambers are provided at various placeswith iron members or partly coated therewith. These members obviouslyparticipate in the reduction or oxidation, ac cordin to the nature ofthe gases passing throng If they have been previously reduced, when thesteam is blown through, they will cause an energetic evolution ofhydrogen which, owing to its great speed of diffusion, will immediatelypenetrate into the smallest pores of the fireproof material, and freethe same from foreign gases. A. portion of hydrogen will be derived fromthe iron of the retorts or columns, when this material is used. I

What ll claim is 1. In a hydrogen apparatus, a heating chamber, avertical casing within the chamher and incommunication therewith at one.end, a pervious ferruginous reaction mass within the casing, means forintroducing and burning gas in said chamber and means for passing draftcurrents of gas and of steam through both the chamber and the casing. 12. In a hydrogen apparatus, a heating chamber and in communicationtherewith at one end, a pervious ferruginousreaction of steam throughboththe chamber and the 3. In a chamber, a vertical iron casing withinthe p its" hydrogen apparatus,a pair of 0011 centric cylinders, aferruginous contact mass in the space between said cylinders, an'inclosing combustion chamber surrounding said cylinders and containinga refractory checkerwork, a combustion chamber surrounded by saidcylinders, means for introducing combustible gas into each combustionchamber, means for introducing air into each chamber, means forintroducing steam into each chamber and means for removing hydrogen fromthe space between the eylin;

ders. v

4: In a hydrogen apparatus, means for] mamtainmg a pervious column offerruno mass within the casing, means for introdue- I ng and burning gasn said chamber and means for passing draft currents of gas and 1nheat-imparting relationship to such col- 'of such iron may be pass umn,means for introducing air into said heating chamber, means for passlnggas through said column and said chamber 1n -success1on, means forpassing steam through said chamber and said column in succession andmeans for removing hydrogen from'said column.

5. In a hydrogen apparatus, an iron container, a pervious ferruginouscharge therein, means for external heating of the container, means forpassing gas through the container into the heating means, means forsupplying air to the heating means for the combustion of such gas, meansfor passing steam through the heating chamber into the container andmeans for removing hydrogen from the container.

6. In 'a hydrogen apparatus, a vertical furnace chamber containing arefractory checkerwork, a vertical iron casing in heatreceivingrelationship to said chamber and in communication therewith at one end,steam introducing means in communication with said chamber at each end,means for introducing air into such chamber, means for introducingcombustible gas into such chamber and into such casing and means forremoving hydrogen from the container.

7. In a hydrogen apparatus, a heating chamber, a container in heatreceiving relationship to said chamber and also havlng directcommunication with said chamber and a porous iron mass in saidcontainer, and means whereby the various draft currents necessary informing hydro en by the aid d successively through both chamber andcontainer.

8. An apparatus for the production of hydrogen by the alternateoxidation and reduction of an iron charge through the agency of steamand a reducing as comprising an an- %etween the walls of chamber formingelements and the other ends are open, a gas-tight inclosed heatingchamber surrounding the reaction space, inlet and outlet pipeconnections for the reducing gas and the steam, and means providingcommunication between these pipes and the heating spaces. 1 v

9. An apparatus for the production of hydrogen by the alternateoxidation and reduction of an iron charge through the agency of steamand a reducing gas comprising an annular reaction space between thewalls,

of two concentric vertical cylinders, the opposite ends of which arejointed gas-tight to chamber forming elements and the other ends open, aheating chamber external to the cylinders and communicating through thereaction space with a heating chamber withm the inner cylinder, inletandoutlet pipe 'ulating the annular passages,

connections for reducing gas and the steam,

means providing communication between these'pipes and the heatingspaces, and a as-tight external casing inclosing all the eating andreaction s aces.

10. An apparatus or the production of hydrogen by the alternateoxidation and reduction of an iron charge through the agency of steamand a reducing gas, comprising a reaction vessel inclosed in a gastightheating space, a firebrickchecker filling in the heatmg space for thestorage of heat, inlet and outlet pipe connections for the reducing gasand the steam, and means for providing communication between these pipesand the heatin spaces.

11. Anapparatus or the production of hydrogen by the alternate oxidationand reduction of an iron charge through the agency of steam and areducing gas, comprising a reaction Vessel inclosed in a gastightheating space, externally opening box-shaped charging and emptyingspaces adjacent to the open end of the reaction space and actingsimultaneously as supply and distribution means for the heating gasesproviding communication between these pipes and the heating spaces.

12. An apparatus for the production of hydrogen by the alternateoxidation and reduction of an iron charge through the agency of steamand a reducing gas, comprising a reaction vessel inclosed in a gastightheating space, externally opening boxshaped charging and emptying spacesadjacent to the open end of the reaction space, radially arranged ductsprojecting into the interior of the heating space, other annularpassages surrounding the box-shaped spaces for the introduction of theheating gases and air of combustion, means for reginlet and outlet pipesfor the reducing gas and the steam, and means for providingcommunication between these pipes and the heating spaces.

13. Apparatus for the production of hydrogen comprising a furnacecontaining ferruginous material, a plurality of regenerators, andsuitable connections for leading gas to and from the said furnace andre,- generators.

14. Apparatus for the production of hydrogen comprising an annularchamber contaimng ferruginous material, two furnace chambers, oneencircling and the other encircled by said annular chamber and suitableconnections for leading gas to and from said annular chamber and saidfurnace chambers.

15. In a hydrogen apparatus,an inner fur- 130 nace chamber having anouter wall, an an nular pervious column of ferruginous reactionmaterialencircling said chamber and means for leading gas and steamthrough the ferruginous reaction material.

16. In a hydrogen apparatus, an. inner furnace chamber having an outerwall, an annular pervious column of ferruginous reaction materialencircling said chamber, means for passing reducing gas and draftcurrents of steam alternately into and through said ferruginous materialand means for removing the hydrogen produced in steaming.

17 In a hydrogen apparatus, two spaced walls of heat transferringmaterial, a mass of ferruginous reaction material retained between saidwalls and combustion chambers on opposite sides of said mass andseparated therefrom by said walls.

18. In a hydrogen apparatus, a mass of ferruginous reaction material, acombustion chamber, a heat transferring partition separating the same,and means for leading draft currents of gas and steam through saidcombustion chamber and through said material and for burning gas in saidcombustion chamber.

19. In a hydrogen apparatus, a wall of refractory material, an ironseptum spaced away therefrom to form a combustion cham-

